X-ray irradiation induced discoloration phosphate glass as well as preparation method and application thereof

Abstract

The invention relates to the technical field of optical glass, in particular to X-ray irradiation induced discoloration phosphate glass and a preparation method and application thereof.The X-ray irradiation induced discoloration phosphate glass changes color through X-ray irradiation, can be bleached through heating, can be colored through X-ray irradiation again after being recovered to the initial state, and comprises the following components by mole percent: 35-45% of NaH2PO4; the content of B2O3 is 40 to 50 percent; 6%-9% of BaF2; and 3 to 6 percent of Sb2O3. The X-ray irradiation induced photochromic glass provided by the invention has relatively high mechanical strength and transparency, the compact network structure endows stable photochromic performance, and the application of the optical glass in the fields of information storage, X-ray detection, aviation, military and the like is expected to be widened. The process is simple, the production cost is relatively low, and the photochromic glass with high optical quality is easy to prepare and obtain.

Description

Technical Field

[0001] The present invention relates to the technical field of optical glass, and in particular to an X-ray irradiation induced color-changing phosphate glass and a preparation method and application thereof. Background Art

[0002] In the current information society, the development of information storage technology is particularly important. Optical storage technology has a long storage time for information, high efficiency and high speed in reading and storing, and has been widely used in recent years. However, new optical storage technologies are still limited by expensive equipment and complex operations. Photochromism refers to the reversible color change of materials under light stimulation, which is a very promising optical storage technology. In current photochromic materials, optical information is mainly recorded on the surface of two-dimensional photochromic storage media, such as ceramics and thin films, which makes it difficult to achieve high storage capacity. Glass is a widely used material. Its "short-range order and long-range disorder" glass network structure gives it excellent stability and good transparency. Compared with 2D storage media, high optical storage capacity can be achieved in photochromic glass by expanding it into transparent 3D bodies. In addition, the irradiation source X-ray has a short wavelength (0.01-10nm) and high energy. Using rays as the information writing source is expected to break through the grating diffraction limit of traditional visible light and achieve high-precision information storage. In addition, in the medical and military fields, radiation protection measures are extremely important. X-rays have a certain killing power on white blood cells in human blood, which reduces the number of white blood cells in human blood, thereby causing the body's immune function to decline, making it easier for pathogens to invade the body and cause disease. Since radiation is in the ultra-short wavelength range and cannot be seen by the naked eye, in order to prevent life safety caused by radiation leakage, it is extremely critical to study new detection technologies.

[0003] Therefore, the present invention prepares a new type of X-ray irradiation color-changing phosphate glass, which changes color when the glass is irradiated with radiation, realizes visual monitoring of radiation, and thus can prevent radiation leakage. In addition, using short-wavelength radiation as an information storage source will hopefully break through the grating diffraction limit and increase the information storage capacity. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing X-ray irradiation-induced color-changing phosphate glass. The X-ray irradiation-induced color-changing glass provided by the present invention has high mechanical strength and transparency, and its dense network structure gives stable color-changing performance, which is expected to broaden the application of optical glass in the fields of information storage, X-ray detection, aviation, military, etc. In addition, the present invention has a simple process, low production cost, and is easy to prepare color-changing glass with high optical quality.

[0005] In order to achieve the above technical purpose and the above technical effect, the present invention is implemented through the following technical scheme: using X-rays to induce structural color change in the glass color, and the degree of structural color change can be used to detect whether X-ray leakage occurs. In addition, the use of a mask plate can realize the writing of optical information.

[0006] An X-ray irradiation induced color-changing phosphate glass, which changes color by X-ray irradiation. The color can be bleached by heating, and after returning to the initial state, it can be colored again by X-ray irradiation. The components thereof, measured in molar percentage, include: NaH2PO4: 35-45%; B2O3: 40-50%; BaF2: 6%-9%; Sb2O3: 3-6%.

[0007] On the other hand, the present invention provides a method for preparing X-ray irradiation induced color-changing phosphate glass, comprising the following steps:

[0008] S1: Mix NaH2PO4, B2O3, BaF2, and Sb2O3 in an agate mortar and grind in air for 10 minutes to make the raw materials fully mixed;

[0009] S2: The mixed raw materials in S1 are placed in a crucible, placed in a high-temperature box furnace at 1150°C for 20 minutes, and then the glass liquid is poured onto a copper plate preheated to 360°C;

[0010] S3: heat treating the glass obtained in S2 in a muffle furnace at 400°C for 2 hours to remove the residual thermal stress of the glass;

[0011] S4: The glass is ground and polished, and then irradiated with different doses of X-rays for different times;

[0012] S5: Put the discolored glass into a muffle furnace and keep it at 350℃ for 15 minutes, then the color can be erased.

[0013] Furthermore, the distribution ratio of each group in the raw material is: NaH2PO4: 35-45%; B2O3: 40-50%; BaF2: 6%-9%; Sb2O3: 3-6%.

[0014] On the other hand, the present invention provides the use of the above glass in X-ray irradiation-induced discoloration.

[0015] Beneficial effects of the present invention:

[0016] The present invention uses X-rays as the information writing source, which improves the capacity and accuracy of the optical storage system. The short wavelength and high energy of X-rays enable it to break through the grating diffraction limit and realize information recording in the three-dimensional space of glass. This significantly expands the capacity of the storage medium relative to the limitations of two-dimensional surface storage. During the irradiation process, the energy of the X-rays causes electron transitions and structural reorganization inside the glass. X-ray irradiation causes the bridging oxygen inside the glass to break, resulting in defects. The defects capture electrons to form "color centers", causing color changes, and the corresponding information is stored in the bulk phase of the glass. This storage capacity provides feasibility for future high-density information storage.

[0017] In the field of radiation protection, color-changing glass provides a solution for visual monitoring. When glass is irradiated by X-rays, the defect centers generated absorb visible light and cause color changes. This process depends on the microstructure and chemical composition of the glass material. After being excited by the energy of the radiation, the local defects or impurities in these materials cause changes in the absorption band. The obvious change in color serves as an indicative signal of the presence of radiation, greatly improving the intuitiveness and accuracy of radiation detection and monitoring, and helping to prevent the hidden dangers of radiation leakage to human health.

[0018] The glass prepared by the present invention can be restored to its initial colorless state after being treated at 350°C, which reflects its reversible color change characteristics. This is because high temperature treatment can eliminate the electronic defects formed during the irradiation process, so that the glass structure returns to a stable state. This characteristic allows the glass to be repeatedly erased and rewritten in information storage applications, enhancing the service life and economy of the material. This process relies on the thermal stability of the glass. Under high temperature conditions, it can provide sufficient energy to overcome the local defect energy barrier and ensure long-term and stable color change cycle performance.

[0019] By adopting a high-temperature solid-phase sintering method to prepare phosphate glass, the present invention combines simple process, strong controllability and excellent material properties. The raw materials are melted at a high temperature of 1150°C to form a uniform glass liquid, and the internal stress is eliminated after rapid cooling to a solid state, ensuring the structural integrity and transparency of the glass. The chemical stability of phosphate glass comes from the strength of the phosphorus-oxygen bonds in its glass network. This "short-range order, long-range disorder" structural characteristic not only ensures the thermal and chemical stability of the glass, but also provides sufficient optical transparency, enabling it to have excellent performance in optical storage and sensing applications.

[0020] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0022] Figure 1 The present invention is a photograph of the glass of the present invention irradiated with X-rays at a dose of 0.00751 Gy / s for different time periods. The glass is colorless and transparent in the initial state, and its color deepens as the irradiation time increases; (a) initial state; (b) 5 min; (c) 10 min; (d) 15 min;

[0023] Figure 2 These are photos of the glass of the present invention after being irradiated with different doses of X-rays for 15 minutes. It can be seen that as the dose increases, the color of the glass deepens; (a) initial state; (b) 0.00092Gy / s; (c) 0.00557Gy / s; (d) 0.00751Gy / s;

[0024] Figure 3 The present invention is the transmission spectrum of the glass before and after the color change due to X-ray irradiation. The transmittance of the glass after irradiation is significantly reduced in the 350-500nm band, indicating that the color change is deepened;

[0025] Figure 4 These are photos of the glass of the present invention at the initial stage, after discoloration, and after heat treatment at 350° C. for 15 minutes and bleaching. DETAILED DESCRIPTION

[0026] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Example 1

[0028] The method for preparing an X-ray irradiation-induced color-changing phosphate glass described in this embodiment includes the following steps:

[0029] S1: Weigh 15 g of raw materials according to the following composition: NaH2PO4: 35%; B2O3: 50%; BaF2: 9%; Sb2O3: 6%; mix the raw materials in an agate mortar and grind them in air for 10 minutes to ensure that the raw materials are fully mixed.

[0030] S2: The mixed raw materials in S1 are loaded into a crucible, and placed in a high-temperature box furnace at a temperature of 1150°C for 20 minutes. Then, the glass liquid is poured onto a copper plate preheated to 360°C, and cooled to room temperature along with the heating furnace.

[0031] S3: The glass obtained in S2 is heat treated in a muffle furnace at 400° C. for 2 hours to remove the residual thermal stress of the glass.

[0032] S4: grinding and polishing the glass;

[0033] S5: The glass was irradiated with X-rays for different time periods, 0 min, 5 min, 10 min, and 15 min. The X-ray dose was 0.00751 Gy / s.

[0034] In this embodiment 1, the glass is irradiated with X-rays for different time periods, such as Figure 1 As shown in (ad), the glass turns yellow after X-ray irradiation. As the irradiation time of transparent colorless glass increases, the color change degree of the glass increases, showing a significant degree of color change, indicating that X-ray induced color-changing glass has excellent X-ray detection capability.

[0035] Example 2

[0036] The method for preparing an X-ray irradiation-induced color-changing phosphate glass described in this embodiment, wherein the X-ray irradiation dose affects the color change degree of the glass, comprises the following steps:

[0037] S1: Weigh 15 g of raw materials according to the following composition: NaH2PO4: 45%; B2O3: 40%; BaF2: 9%; Sb2O3: 6%; mix the raw materials in an agate mortar and grind them in air for 10 minutes to ensure that the raw materials are fully mixed.

[0038] S2: The mixed raw materials in S1 are loaded into a crucible, and placed in a high-temperature box furnace at a temperature of 1150°C for 20 minutes. Then, the glass liquid is poured onto a copper plate preheated to 360°C, and cooled to room temperature along with the heating furnace.

[0039] S3: The glass obtained in S2 is heat treated in a muffle furnace at 400° C. for 2 hours to remove the residual thermal stress of the glass.

[0040] S4: grinding and polishing the glass;

[0041] S5: Determine the X-ray irradiation time to be 15 minutes and change different X-ray irradiation doses.

[0042] S6: The glass prepared in S4 is tested for its transmission spectrum before and after discoloration by X-ray irradiation.

[0043] In this embodiment 2, the X-ray irradiation time is determined and the irradiation dose is changed, such as Figure 2 As shown in (ad), the transparent glass changes color more with the increase of irradiation dose, indicating that the glass is responsive to the X-ray irradiation dose, and further indicating that the glass prepared by the present invention can realize X-ray detection and optical information storage by using a mask. Then the transmission spectrum of the glass before and after the color change was tested, as shown in FIG. Figure 3 As shown, the transmittance of the glass decreases after color change, indicating the excellent X-ray irradiation color change performance of the glass.

[0044] Example 3

[0045] The method for preparing an X-ray irradiation-induced color-changing phosphate glass described in this embodiment, wherein the glass exhibits reversible X-ray irradiation color-changing properties, comprises the following steps:

[0046] S1: Weigh 15 g of raw materials according to the following composition: NaH2PO4: 43%; B2O3: 48%; BaF2: 6%; Sb2O3: 3%; mix the raw materials in an agate mortar and grind them in air for 10 minutes to ensure that the raw materials are fully mixed.

[0047] S2: The mixed raw materials in S1 are loaded into a crucible, and placed in a high-temperature box furnace at a temperature of 1150°C for 20 minutes. Then, the glass liquid is poured onto a copper plate preheated to 360°C, and cooled to room temperature along with the heating furnace.

[0048] S3: The glass obtained in S2 is heat treated in a muffle furnace at 400° C. for 2 hours to remove the residual thermal stress of the glass.

[0049] S4: grinding and polishing the glass;

[0050] S5: Determine that the X-ray irradiation time is 15 minutes, the irradiation dose is 0.00751 Gy / s, and irradiate the glass.

[0051] S6: The discolored glass is placed in a muffle furnace at 350°C, kept warm for 15 minutes, and then thermally bleached.

[0052] In this embodiment 3, the X-ray irradiation time and irradiation dose are determined, such as Figure 4 As shown in the figure, the transparent glass turns yellow under X-ray irradiation, and then the color can be bleached by heat treatment, showing excellent reversible X-ray color change performance. This reversible color-changing glass promotes its application in the fields of X-ray detection, reversible information storage, and radiation protection.

[0053] The transparent X-ray irradiation-induced color-changing transparent glass obtained in Examples 1-3 of the present invention, wherein the sintering temperature is 1150° C. and the time is 20 min, exhibits different degrees of color change under irradiation with different X-ray doses and irradiation times, and the color change can be eliminated by heat treatment, showing excellent reversibility. The X-ray irradiation color-changing glass, due to its excellent X-ray response capability, shows great application prospects in the fields of information storage, X-ray dosimeters, aviation, and military.

[0054] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An X-ray irradiation-induced color-changing phosphate glass, characterized in that: The glass changes color by X-ray irradiation, and the color can be bleached by heating. After returning to the initial state, it can be colored again by X-ray irradiation. Its components, in terms of molar percentage, include: NaH2PO4: 35-45%; B2O3: 40~50%; BaF2: 6%~9%; Sb2O3: 3~6%.

2. The method for preparing glass according to claim 1, characterized in that: The following steps are involved: S1: Mix NaH2PO4, B2O3, BaF2, and Sb2O3 in an agate mortar and grind in air for 10 minutes to make the raw materials fully mixed; S2: The mixed raw materials in S1 are placed in a crucible, placed in a high-temperature box furnace at 1150°C for 20 minutes, and then the glass liquid is poured onto a copper plate preheated to 360°C; S3: heat treating the glass obtained in S2 in a muffle furnace at 400°C for 2 hours to remove the residual thermal stress of the glass; S4: The glass is ground and polished, and then irradiated with different doses of X-rays for different times; S5: Put the discolored glass into a muffle furnace and keep it at 350℃ for 15 minutes, then the color can be erased.

3. The preparation method according to claim 2, characterized in that: The distribution ratio of each group in the raw material is: NaH2PO4: 35-45%; B2O3: 40-50%; BaF2: 6%-9%; Sb2O3: 3-6%.

4. Use of the glass as claimed in claim 1 in X-ray irradiation-induced discoloration.

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